Water-insoluble azo-dyestuffs and fiber dyed therewith



wherein R presents'aradicalof he benzene, 7 l

" 2'31- hydroxynaphthoyl.2-aminoe6+alkoxy-naph- Patented Nov. 14, 1 9331 1 9? V 'WATER-INSOLUBLE AZO-DYESTUFFS AND FIBER. DYED THEREWITHLeopold Laska and, Arthur Zitscher,.0ffenbachon-the-Main, Germany,assignors to General a Aniline Works, Inc., New York, N. Y., a corpora-'tion of Delaware N oDraw ing. Application January 12, 1933, Serial No.651,448 ,'and in Germany January 18, 1932 10 Claims. The presentinvention relates vto newllwate rinsoluble vazodyestuffs and tofiber-dyed therewith, more particularly it relates to compounds of thefollowing general formula:

' N =N R" naphthalene or anthraquinone series;

We have found that valuable water-insoluble azo-dyestufis are obtainableby combining a diazo tetrazoordiazoazo-eompound which does not containany grouplending solubility: such as the sulfonic acid or carboxylicacid group with a thalene, either in substance, on the fiber or on anyof the usual substrata adapted for the production of lakes.

It issurprisingthatf the dyestuifs obtainable according to the presentinvention, when compared with the dyestuff'sfwhichi are, obtained byusing 2 3" hydroxynaphthoyl-Z-amino-naphthalene and 2'3hydroxynaphthoylj2,jamino-3- methoxy-naphthalene, respectively, are distinguished byanincreasedfastnessto light, ,j j

dium bicarbonate, thereupon, thefyarn is rinsed and soaped whilehotf" VThe 2f3'-hydroxynaphthoyl-2-amino-6-alkoxynaphthalenes may beobtained bycondensing 2.3-,

hydroxyn'aphthoic acid with I 2-amino-6-allroxy-v naphthalenes accordingto] one of the usual methods. Y i

The following examples serve to" illustrate the inventionQbutfthe'y arenot intended to limit it thereto, the parts beingby weight unlessotherwise stated:'- 1 a W (1) Well boiled and dried cotton yarn ispadded 'with asolution containing per liter 7 I 2'3 hydroxyna'phthoyl- Z-ama 2.25 gramsof ino-6-n'1ethoxynaphthalene, cc;

j of ust d isq iion 91.3 Be" and. a I a. 10 cc. 'of'Turkey'red-oil,

v the yarn is thoroughly squeezed. and developed in v a diazo-solutionwhich contains'per liter 1.21'grams of l amino 2A dimethylbenzene v andwhich has been neutralized by :means of so- A saturated red dyeing ofvery good fastness to light is thus obtained. 7

The dyestufi corresponds to the following formula: I

v (2) "developing dehydrated cotton yarn which has been impregnated asdescribed in example 1 in a liter r V 1.76 grams of1-amino-4-methyl-2.3-dichlorobenzene, and. which has been neutralized bymeans of sodium acetate, and by rinsing and soaping the yarn, there isobtained a bluishqeddyeing of very good fastnessto light. r

(3) l2.75'p'arts .of I-aminmB-chlorobenZene are dissolved in;34.2,parts1of hydrochloric acid of -B and '250 parts; of -water 'andthewhole is diazotized at" about 10 Q. by a'ddition'of a'solution,of7;pa'rts'"of sodiumnitrite in 100 parts of Water.- The diazo-solutionisrun into a solution of '36 ,'parts' of 2 3'-hydroXynaphthoyl-2-amino-6-methoxy-naphthalene, in [70 0 parts of Water and 244 parts of Jcaustic soda solution of -40-B, to-which solution there has been addedthe quantity "or sodium acetate .sufiicient for T'of Turkey red oil.After the coupling .hasbeen diazo" solution, which contains per bindingthe excess'of mineral acid and 15 parts finished, the dyestuif formedis" filteredby suction and washed well. It may ;be used for thepreparation of pigments, advantageously, *in the form, of a paste; Thedyestuff forms in the state ayellowish-red powder.

It yieldsflwh'en prepared, in the usual manner a on a substratum areddish orange pigment dye- (4) Cotton yarn which 'hasappropriately beentreated is impregnated with. a paddingrsolution which has been preparedin the usual manner and which containsper liter j 2 grams of2'3-hydroxynaphthoyl-2-amino-6- ethoxy-naphthalene' and, afterhavingdehydrated the yarn, it isdeveloped'in a dia'zo solutionwhichcontains per zone OCH:

The dyestuffs may also beprepared on other fibers, as, for instance, onregenerated cellulose or on animal fibers, and may also bev applied inthe usual printing processes. 1

By using other diazo-, tetrazoor-diazoazocompounds, the process of thepresent invention may be carried out in like manner.

The following table indicates a number of other combinations obtainableaccording to the pres;

ent process but it does not comprise all possibilities for thepreparation of dyestuffs by using different components; it, therefore,is not intended to limit the invention to the dyestuffs Y i mentionedtherein:

1.68 grams of 1-amino-2-methoxy-4-nitrobenappended claims do not containany substituents which are known to render organic compounds soluble inwater or alkalies and to tend to depreciate thefastness of the dyestuffsto alkalies. 'Substituents of this kind are, for instance,

the sulfonic acid and carboxylic acid group.

i We claim:

*1; The water-insoluble azo-dyestuffs of the following 1 general formulaCO-NH 'o-aik i wherein R represents a radical of the benzene,

naphthalene or anthraquinone series, yielding, when producedon thefiber, dyeings the shades I of which vary from red to blue to black andbeing distinguished by good iastness properties, particularly by a goodfastness tolight.

2. The water-insoluble azo-dyestuffs of the following general formula:

na -R OOHa wherein It represents a radical of the. benzene Diazotizingcomponent Coupling component Tint (1) 1-amino- 3-ch1orobenzene2'3.-hydroxynaphthoyl-2-amino-6-methoxynophthalene Reddish-orange (2)l-ann'n0-2.5-dich1orobenzene d Brownish-red g3) 1-anino-2A.fi-trichlorobenzene .do Orange-brown 4)1-amino-2-methyl-5-ch1orobenzene do Red (5)1-amino-2-methyl-4-ch1orobenzene do Saturated red (6)1-amino-2-methyl-4-bromo-5-chlorob do Deep bluish-red (7)1-amino-3-methyl-4.o-dichlorobenzenem; do 1 Bluish-red (8)1-amino-2-methoxy-5-ch1orobenzene -do Saturated red (9)1-amino-2-phenoxy-5-ch1orobenzene do Yellowish-red (10)1-amino-2-nitrob'en one do Brownish-red (l1) l-amino-S-nitrobenzeneYellowish-red (12) Lamina-4-chloro-2-nitrobenzene Brownish-red (l3)l-arnino-2-methyl-5-nitroben1 ne Clear yellowish-red (14)1-amino-4-methyl-2-nitrobenzeue Deep bluish-red (15)l-amino-2-methyl-4-nitrob fl1ene Brownish-red (16) l-amino-2-methoxy-5nitrobenzene do Red (17) 1-amino-2-methoxy-4-nitrobenzene do Bordeaux(18) 1-amino-4-nitronaphthalano do Saturated Bordeaux (19)'l-amino-S-nitrouaphthalene L; Bordeaux (20)l-amino-5.8-dichloro-naphthalene Do. (21)4-zgmiuo-3-methoxy-6.4'-(limethyl-2-nitroazodo Blackish-currant enzene.(22) l'-aminoauthraquinone;; '(io 'Brownish-red (23) ,1-amino-4-benzoyl-amino-2.5-dimethoxyben- Reddish-dark blue zene. i (24)4-aniino-2.5-dimethoxy-4 nitroazoben Pne Violet-black (25)1-amino-2.5-dichlorobenzener Brownish-red (26)l,-amino-2.4,5-trichlorobenzene Reddish-brown (27)1-amino-2-methyl-4bromo-5-ehl Yellowish-red (28)l-amino-2-methoxy-5-chlorobenzene Bluish-red (29)l-amino-2-phenoxy-5-chlorobenzeuel Yellowish-red (30)l-amino-4-chloro-2-nitrobenzene Yellowish-Bordeaux (31)1-amiuo-4-methyl-2enitrobenzene. Bordeaux '(32)l-arnino-2-methyl-i-nitrobe11ze11e Do; (33) lamina! (2-ethoxy-phenyl lazo)-napl1thado Black one. v

which dyestuffsare insoluble in water and alkalies, it "is to beunderstood'that the aromatic nuclei of the general formulae appearing inthea series, yielding, when produced on the fiber, dye- 3.Thewater-insoluble azo-dyestufli of the following formula: I

OCH:

yielding, when produced on the fiber, a Bordeaux dyeing and beingdistinguished-by good fastness properties, particularly by a goodfastness to light.

4. The water-insoluble azo-dyestuff of' the following formula: V r

CONH' OCH:

yielding, when produced on the fiber, a clear yellow-red dyeing andbeing distinguished by 3 good fastness' properties, particularly byagood fastness t0.light.

5. The water-insoluble azo-dyestufl of the following .formula:

OOH

yielding, when produced on the fiber. an orangebrown. dyeing and beingdistinguished by good LEoPoLnLAsKA." I ARTHUR ZITSCHER. I

